KR100886580B1 - Coating method in mold of hydrogel product - Google Patents

Abstract

In the present invention, there is provided a method for coating a hydrogel and silicone hydrogel product, and a product produced by the method, wherein the coating is first applied to the mold surface and the product forming material is cured to form a product. The method of the present invention can more easily control the thickness and uniformity of the coating than known coating methods.

Mold Surfaces, Contact Lenses, Hydrogels, Silicone Hydrogel Products, Coating Compositions

Description

Coating method for hydrogel products {Method for in mold coating hydrogel articles}             

The present invention relates to coated articles comprising, but not limited to, contact lenses. In particular, the present invention relates to coated hydrogels and silicone-hydrogel products formed by curing the reaction mixture of the product forming material in a mold whose mold surface has a coating film.

It is known to use hydrogels to form articles such as contact lenses. It is also known to increase the oxygen permeability of hydrogels by adding silicone containing monomers to the hydrogel formulation to produce silicone hydrogels.

Typically, to increase the surface wettability of hydrogel and silicone hydrogel products, it is desirable to coat the product with a hydrophilic coating. Many hydrophilic coatings and methods of making them are known. For example, it is known to apply a coating to a silicone hydrogel lens using gas plasma. This coating method has the disadvantage that it is required to dewater the lens before applying the plasma treatment, and this treatment must be performed under vacuum conditions.

Otherwise, it is known to use a solution or solvent base coating to cover the lens. However, this coating method, like plasma treatment, adds several steps to the lens manufacturing process and generates a large amount of waste. In addition, uniform application of solution-based coatings to the lens surface requires very precise process control.

Also described is a method of applying the coating to a mold in which the lens material is dispersed. However, this method has proven successful only in non-silicone hydrogel materials. Accordingly, there is a need for a coating method for coating hydrogel and silicone hydrogel lenses that addresses one or more of these shortcomings.

In the present invention, a method of coating a hydrogel and silicone hydrogel product, and a product manufactured by the method, wherein the uncured coating is first applied to the mold surface of the mold and the product forming material is cured to form a product. Is provided. Thus, the product is coated during the curing of the material to be formed, eliminating the need for additional processing steps after the curing is complete. In addition, the method of the present invention makes it easier to control the thickness and uniformity of the coating than known coating methods. Finally, since the method of the present invention does not depend on the specific reaction chemistry for attaching the coating to the lens, as in known coating methods, various coatings that are not adequately achievable using known coating methods are also possible. Done.

The present invention provides a method of coating a mold or mold half of a mold surface with a coating effective amount of a high molecular weight coating composition (a), the hydrogel monomer, the silicone-containing hydrogel monomer or a combination thereof, or A method of coating a product, comprising, consisting essentially of, or consisting of (b) dispersing in a mold and (c) curing under conditions suitable for forming a product coated with the coating composition. To provide.

The present invention can be used to make a variety of coated articles. Preferably, the present invention is used in the manufacture of ophthalmic lenses including, but not limited to, contact lenses, intraocular lenses and superimposed lenses. More preferably, the present invention is used for the manufacture of contact lenses.

For the purposes of the present invention, "molding surface" means the surface used to form the surface of the article. Typically, shaped articles are formed in a mold or between two half molds. The mold or half mold used to form the product has an inner surface, a mold surface and an outer non-molding surface. One of ordinary skill in the art will appreciate that the mold surface can be made in the dimensions and surface shapes required to form the desired molded article.

By "high molecular weight" is meant a molecular weight ("Mw") high enough to prevent the coating from dissolving in the monomer mixture used. For the purposes of the present invention, the molecular weight is preferably modeled by a light scattering detector and a highly sensitive diffraction index detector such as Polymer Labs, using Gel Permeation Chromatography ("GPC"). Measure with GPC was carried out using a 5 μm linear column of phenogel equipped with a protective column of the same component and 0.5% by weight of lithium bromide in dimethyl formamide as eluent. The flow rate is 0.5 ml per minute at an injection volume of about 10 to about 20 μl. The exact Mw used will depend upon the coating chosen and the monomer mixture used. In a preferred embodiment, the Mw of the coating is greater than about 300 kD.

Alternatively, useful coating compositions have a viscosity at 25 ° C. of about 1 cP, preferably at least about 4 cP. For the purposes of the present invention, the viscosity is preferably determined by dissolving the monomer or polymer component in a suitable solvent and measuring the viscosity at a shear rate of 40 / s. If the product forming material is a silicone hydrogel, 1.00% by weight of a 1: 1 solvent mixture of ethanol: ethyl acetate or isopropanol: isopropyl lactate is preferably used.

By "hydrogel monomer" is meant a material which is elastic after curing and hydration and has a water content of at least about 20% by weight. By "silicone containing hydrogel monomer" is meant a hydrogel monomer containing at least one silicone group.

For the purposes of the present invention, "monomer" means a compound having a number average molecular weight of less than about 700, which is a medium to high molecular weight compound or polymer having a number average molecular weight of greater than about 700 and further containing a polymerizable functional group. (Which is often referred to as macromonomers or macromers). "Monomers" include monomers, macromonomers, macromers and partial polymers. A "partial polymer" is a partially polymerized monomer or further polymerizable monomer.

In a preferred embodiment, the present invention comprises the steps of (a) coating a mold or semi-mold mold surface with a coating effective amount of a high molecular weight hydrophilic coating composition, wherein the hydrogel monomer, silicone-containing hydrogel monomer or combination thereof is applied to the mold or semi-mold; Hydrogel and silicone containing hydrogel, comprising, consisting essentially of, or consisting of, dispersing (b) and curing (c) under conditions suitable to form a product coated with the coating composition. Provides a method of coating the product. For the purposes of the present invention, "hydrophilic" means a material which, when polymerized, has a prior dynamic contact angle of less than about 100 ° in physiological saline.

In a more preferred embodiment, the present invention is used in the manufacture of physiologically compatible contact lenses, thus coating a mold or semi-mold mold surface with a coating effective amount of a high molecular weight hydrophilic coating composition (a), hydrogel monomer, silicone containing (B) dispersing the hydrogel monomer or combination thereof in a mold or semi-mould, and curing under conditions suitable for the formation of a contact lens coated with the coating composition, or consisting essentially of these steps, or And it provides a method of coating a contact lens showing a physiological compatibility, consisting of these steps.

"Physiologically compatible" or "physiologically compatible" means that the lens exhibits clinical performance equivalent to or better than that of the etafilcon A lens in terms of ocular wetting and surface deposition resistance. Ocular wettability is determined by measuring a non-irritating tear shedding time using a tear region located between the slit lamp microscope and the eye of the lens wearer. The lens wearer blinks the eye and keeps the eye open while observing the eye through the slit lamp, typically at about 16-20 magnification. The time between blinking and the first observed non-wetting state of the lens surface is the time of non-irritation tearing. The non-irritating tear shedding time for the lens of the present invention is equivalent to or greater than that of the etafilcon A lens, and equal to or greater than about 5 to about 10 seconds. Preferably, the lens of the present invention exhibits a non-irritating tearing time of about 7 to about 10 seconds.

Surface deposition resistance is achieved by scanning the entire lens into the eye using a slit lamp at a beam width and height (typically about 2 mm wide and about 6 mm high beam height) installed at about 16 to about 20 magnification and approximately half of the corneal diameter. Measurements are made on both the front and rear lens surfaces. Deposits can appear as discrete deposits (eg jelly bumps) or oily patches or films and can be removed from the lens during flickering or Josephson Push-Up tests. Grade 0 is where no deposition is observed, grade 1 is about 1 to about 5% of the lens surface deposited, grade 2 is about 6 to about 15% is deposited, and about 16 to about 25 Grade 3 is grade 3 and at least about 26% is grade 4 Surface deposition for the lenses of the invention is equivalent to or greater than that of the etafilcon A lens, meaning that less than about 15% of the clinical population may have a grade 3 or greater deposition after one week of wear.

Coating compositions useful in the present invention may contain various monomers and polymers known in the art. Preferably poly (vinyl alcohol), polyethylene oxide, poly (2-hydroxyethyl methacrylate), poly (methyl methacrylate), poly (acrylic acid), poly (methacrylic acid), poly (maleic acid), Poly (itaconic acid), poly (acrylamide), poly (methacrylamide), poly (dimethylacrylamide), poly (glycerol methacrylate), polystyrene sulfonic acid, polysulfonate polymer, poly (vinyl pyrrolidone) , Carboxymethylated polymers such as carboxymethylcellulose, polysaccharides, glucose amino glycans, polylactic acid, polyglycolic acid, block or random copolymers of those described above, and mixtures thereof. Preferably, poly (2-hydroxyethyl methacrylate), poly (vinyl pyrrolidone), poly (acrylic acid), poly (methacrylic acid), poly (meth) acrylamide or poly (acrylamide) are used do. More preferably, poly (2-hydroxyethyl methacrylate) is used.

Such coating compositions may comprise a low boiling point or less than about 90 ° C. solvent and a high boiling point or more than about 100 ° C. solvent, preferably for spin coating. Suitable low boiling solvents include, but are not limited to, n-methyl pyrrolidone, acetone, chloroform and alcohols such as methanol, ethanol, isopropanol, tert-butanol, and the like. Useful high boiling solvents include, but are not limited to, methyl-, ethyl- and isopropyl lactate, ethylene and (poly) ethylene glycol, propylene glycol, n-methyl pyrrolidone, dimethyl formamide, tetrahydrogeraniol , 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 3-methyl-3-pentanol, dimethyl-3-octanol, 3-methoxy-1-butanol, 1,2 and 1 , 4-butanediol, 1,3-hexanediol, water and the like. Typically, the ratio of low boiling point solvent to high boiling point solvent will be about 1: 1 at room temperature.

In addition, the coating composition may comprise and preferably include one or more surfactants. Suitable surfactants include, but are not limited to, anionic surfactants such as carboxylic acid salts, sulfonic acid salts, sulfates, phosphoric acid and polyphosphate esters, cationic surfactants such as long chain amines and salts thereof, diamines and Polyamines and salts thereof, quaternary ammonium salts, amine oxides, nonionic surfactants such as polyoxyethylenated alkylphenols, alkyl phenol ethoxylates, polyoxyethylenated straight alcohols, polyethoxylated polyoxypropylene glycols , Polyethoxylated polydimethylsiloxane copolymers, fluorinated alkane ethoxylate copolymers and long chain carboxylic acid esters), zwitterionic surfactants such as pH sensitive and pH insensitive surfactants, and combinations thereof are used. . The specific type and amount of surfactant used will depend upon the other components and mold surface of the coating composition used. Typically, from about 0.001% to about 5% by weight, based on the total weight of the coating composition, can be used.

In a first step of the process of the invention, a coating effective amount of a suitable coating composition is coated on a mold or semi-mold mold surface. Preferably, all outer surfaces of the article are covered, and therefore preferably all or substantially the entire mold surface of all of the molds is covered. One of ordinary skill in the art will appreciate that one of the mold surfaces of the mold can be coated with the same or different coating as used for the mold surface of the other mold.

The thickness of the coating composition relative to the mold surface of the mold should be such that when dried, a product with a surface roughness of acceptance level is produced. In embodiments where the article is a contact lens, preferably the peak to peak surface roughness of the hydrated lens is preferably less than about 500 nm. Thus, the effective amount of coating refers to the dry film thickness of the coating composition on the mold surface, which can produce a hydrated product having a surface roughness of the pass level, in the case of contact lenses, preferably a peak to peak surface roughness of a hydrated lens of about 500 nm. Means an amount of coating composition sufficient to provide. More preferably, for contact lens embodiments, the amount of coating composition used is sufficient to produce a dry film thickness of about 5 to about 70 nm, preferably about 5 to about 50 nm, more preferably about 20 to about 40 nm. to be.

The coating composition may be applied to the mold surface by any suitable method including, but not limited to, compression, swabbing, spray coating, ink jet printing, aerosolization, spraying, dip coating, spin coating, and the like, and combinations thereof. have. Preferably, spin coating is used. In addition, the coating is preferably made dry or non-tacky before the product forming material is introduced into the mold. Drying can be carried out using any suitable method, but is preferably carried out at a temperature below the glass transition temperature ("Tg") of the mold material in air or under vacuum and then at a temperature below the Tg of the mold material in a nitrogen blanket. Equilibrate under During the vacuum exposure process, it is desirable to use cold traps or other filters to prevent contamination of the mold.

In the spin coating method, the coating composition preferably has a surface tension lower than the surface tension of the surface energy of the mold surface. More preferably, the surface tension of the coating composition is at least about 3 dyne / cm lower than the surface tension of the surface energy of the applied mold surface when measured at the coating application temperature. Most preferably, the surface tension of the coating composition is at least 8 dyne / cm below the surface tension of the surface energy of the mold surface.

In a preferred spin coating method for use in forming contact lenses, spin coating is used to deposit a dry thickness coating of about 5 to about 70 nm on the mold surface of the mold. If the surface tension of the coating, when measured at the coating application temperature, differs by at least about 8 dyne / cm from the surface energy of the mold, a suitable spin profile is about spinning for at least about 3 seconds using about 2 to about 20 microliters of coating composition. 6,000 to about 8,000 rpm. If the surface tension difference is less than about 8 dyne / cm, the mold is spun at about 3,000 to about 5,000 rpm using about 2 to about 10 microliters of coating composition, and then the mold is about 7,000 to about 10,000 for at least about 3 seconds before stopping. Spin at rpm.

Excess coating that accumulates at the edges of the mold must be removed, and this removal is performed by any convenient method including, but not limited to, excess swabbing, excess removal or cleaning with vacuum solvents, or pressurized air jets. can do. Preferably, excess is removed using an air jet. When using an air jet, spin coating is initiated prior to the operation of the jet, preferably it is important that the air jet pressure is equal to or greater than about 10 psi.

In a second step of the process of the invention, the product forming material, which is a mixture comprising a hydrogel monomer, a silicone containing hydrogel monomer or a combination thereof, is dispersed in a mold or semi-mould. Useful hydrogel monomers are known and include, but are not limited to, hydrophilic monomers, preferably acrylic or vinyl containing hydrophilic monomers. Hydrogel monomers that may be used include, but are not limited to, polyoxyethylene polyols in which one or more terminal hydroxy groups are substituted with functional groups containing polymerizable double bonds. Suitable monomers include, but are not limited to, isocyanatoethyl methacrylate in order to produce polyethylene polyols in which one or more terminally polymerizable olefinic groups are bonded to the polyethylene polyol via a bonding moiety such as a carbamate or ester group. Polyethylene glycol, ethoxylated alkyl glucoside and ethoxylated bisphenol A, which react with one or more equivalents of terminal blocking groups such as methacrylic anhydride, methacryloyl chloride, vinylbenzoyl chloride, and the like. Further examples of hydrogel monomers include, but are not limited to, hydrophilic vinyl carbonate or vinyl carbamate monomers described in US Pat. No. 5,070,215 and hydrophilic oxazolone monomers described in US Pat. No. 4,910,277, Wherein both of the above U.S. patents are hereby incorporated by reference in their entirety.

"Vinyl type" or "vinyl containing" monomers refer to monomers containing vinyl groups (-CH = CH ₂ ) and are generally highly reactive. Such hydrophilic vinyl containing monomers are known to polymerize relatively easily. "Acrylic type" or "acrylic containing" monomers are monomers containing an acrylic group (CH ₂ = CRCOX), wherein R is H or CH ₃ and X is O or N and is known to be readily polymerized. N, N-dimethyl acrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate, 2-hydroxyethyl methacrylamide, polyethylene glycol monomethacryl Latex, methacrylic acid and acrylic acid.

Preferred hydrogel monomers used in the preparation of silicone containing hydrogels useful in the present invention may be acrylic or vinyl containing monomers and the monomers themselves may be crosslinkers. Useful vinyl containing monomers include, but are not limited to, N-vinyl lactams such as N-vinyl pyrrolidone (“NVP”), N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl Acetamide, N-vinyl-N-ethyl formamide and N-vinyl formamide are included, with N-vinyl pyrrolidone being preferred.

Particularly useful silicone containing hydrogel monomers include those containing two or more [—Si—O—] repeat units. Preferably, the total Si and bound O are present in the silicon-containing monomer in an amount of at least about 20% by weight, more preferably at least about 30% by weight, based on the total molecular weight of the silicon-containing monomer.

Preferred silicone-containing hydrogel monomers are compounds of formula (I).

In Formula I above,

R ₅₁ is H or CH ₃ ,

q is 1, 2 or 3,

For each q, R ₅₂ , R ₅₃ and R ₅₄ are independently alkyl or aromatic, preferably ethyl, methyl, benzyl, phenyl, or siloxane chains comprising 1 to 100 Si—O repeat units,

p is 1 to 10,

r is (3-q),

X is O or NR ₅₅ , wherein R ₅₅ is H or an alkyl group having 1 to 4 carbon atoms,

a is 0 or 1,

L is preferably a divalent bonding group comprising 2 to 5 carbon atoms and optionally comprising an ether or hydroxyl group, for example a polyethylene glycol chain. Examples of such monomers include, but are not limited to, methacryloxypropylbis (trimethylsiloxy) methylsilane, methacryloxypropyltris (trimethylsiloxy) methylsilane, methacryloxypropylpentamethyldisiloxane, and (3- Methacryloxy-2-hydroxypropyloxy) propylbis (trimethylsiloxy) methylsilane.

It is more preferred to use straight chain monoalkyl terminated polydimethylsiloxanes (“mPDMS”) as shown in formula (II).

In Formula II above,

b is a distribution with the most frequently occurring b value, wherein the b value is 0 to 100, preferably 8 to 10,

R ₅₈ is a group containing free radically polymerizable ethylenically unsaturated moieties, preferably methacrylate, methacrylamide, styryl, N-vinyl amide, N-vinyl lactam, vinyl carbonate, vinyl carbamate, maleate or Fumarate,

Each R ₅₉ is independently an alkyl or aryl group which may be further substituted by alcohol, amine, ketone, carboxylic acid or ether group, preferably an unsubstituted alkyl or aryl group, more preferably methyl,

R ₆₀ is C ₁ which may include an alkyl or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether group, preferably an unsubstituted alkyl or aryl group, more preferably a hetero atom -C ₁₀ aliphatic or aromatic group, even more preferably C _3-8 alkyl group, most preferably butyl.

Additional silicone containing hydrogel monomers may be combined with silicone containing hydrogel monomers of formula (I) and formula (II) to form the product produced by the process of the invention. All known silicone-containing hydrogel monomers useful for the preparation of silicone-containing hydrogels can be used in combination with the silicone-containing hydrogel monomers of Formula I and Formula II to form the products of the present invention. Many silicone-containing hydrogel monomers useful for this purpose are described in US Pat. No. 6,020,445, which is hereby incorporated by reference in its entirety. Further useful silicone-containing hydrogel monomers in combination with the silicone-containing monomer of formula (I) to form the silicone hydrogel of the present invention are the hydroxyalkylamines described in US Pat. No. 5,962,548, which is incorporated herein by reference in its entirety. It is a functional silicone containing monomer. Preferred silicone-containing straight or branched chain hydroxyalkylamine functional monomers include block or random monomers of formula III.

In Formula III above,

n and m, respectively, are the distributions with the most frequently occurring respective n and m values, where n values are 0 to 500, m values are 0 to 500, and (n + m) is 10 to 500, more preferably Is 20 to 250,

R ₂ , R ₄ , R ₅ , R ₆ and R ₇ are independently alkyl or aryl groups, preferably unsubstituted alkyl or which may be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups Aryl group,

R ₁ , R ₃ and R ₈ are independently alkyl or aryl groups, preferably unsubstituted alkyl or aryl groups, which may be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, or Nitrogen-containing structure,

At least one of R ₁ , R ₃ and R ₈ is according to formula IV.

In Formula IV above,

R ₉ is a divalent alkyl group, for example-(CH ₂ ) _s where s is 1 to 10, preferably 3 to 6, most preferably 3,

R ₁₀ and R ₁₁ are independently H, alkyl or aryl groups which may be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, or have the structure of formula (V).

In Formula V above,                 

R ₁₄ is H, or a polymerizable group comprising acryloyl, methacryloyl, styryl, vinyl, allyl or N-vinyl lactam, preferably H or methacryloyl,

R ₁₆ is an H, alkyl or aryl group which may be further substituted by alcohol, ester, amine, ketone, carboxylic acid or ether group, or an acrylate, methacrylate, styryl, vinyl, allyl or N-vinyl lactam Alkyl groups substituted with polymerizable groups, preferably alcohols or methacrylates,

R ₁₂ , R ₁₃ and R ₁₅ are independently H, alkyl or aryl which may be further substituted by alcohol, ester, amine, ketone, carboxylic acid or ether group,

R ₁₂ and R ₁₅ and R ₁₅ and R ₁₃ may be bonded together to form a ring structure,

At least a portion of the group of formula IV on the monomer comprises a polymerizable group. R ₁₂ , R ₁₃ and R ₁₅ are preferably H.

In another embodiment, silicone-containing hydrogel mixtures useful in the present invention consisting of silicone-containing hydrogel monomers of either or both of Formula I and Formula II may also contain hydrophilic monomers. The hydrophilic monomer optionally used may be any known hydrophilic monomer useful for the preparation of hydrogels.

Preferred hydrophilic monomers used in the preparation of the silicone-containing hydrogel monomers of the invention may be acrylic or vinyl-containing monomers. Such monomers may themselves be used as crosslinkers. Hydrophilic vinyl-containing monomers that can be incorporated into the silicone-containing hydrogels of the invention include N-vinyl lactate (e.g. NVP), N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N- Monomers, such as vinyl-N-ethyl formamide and N-vinyl formamide, are contained and NVP is preferable.

Other hydrophilic monomers that may be used in the present invention include polyoxyethylene polyols in which one or more terminal hydroxyl groups are substituted with functional groups containing polymerizable double bonds. Examples thereof include isocyanatoethyl methacrylate ("IEM"), in order to produce polyethylene polyols in which one or more terminally polymerizable olefinic groups are bonded to the polyethylene polyol via a bonding moiety such as a carbamate or ester group, Polyethylene glycol, ethoxylated alkyl glucoside and ethoxylated bisphenol A which react with one or more equivalents of terminal blocking groups such as methacrylic anhydride, methacryloyl chloride, vinylbenzoyl chloride and the like.

Further examples include the hydrophilic vinyl carbonate or vinyl carbamate described in US Pat. No. 5,070,215 and the hydrophilic oxazolone monomer described in US Pat. No. 4,910,277, wherein both of the above US patents are herein incorporated by reference in their entirety. It is cited by reference. Other suitable hydrophilic monomers will be apparent to those of ordinary skill in the art.

More preferred hydrophilic monomers that can be incorporated into the polymers of the invention include N, N-dimethylacrylamide ("DMA"), 2-hydroxyethyl methacrylate ("HEMA"), glycerol methacrylate, 2-hydroxy Hydrophilic monomers, such as ethyl methacrylamide, NVP, polyethylene glycol monomethacrylate, methacrylic acid and acrylic acid, are included, with DMA being most preferred.

Other monomers that may be present in the reaction mixture used to form the hydrogel or silicone containing hydrogel monomer mixture useful in the present invention include ultraviolet absorbing monomers, reactive colorants, pigments and the like. Additional processing aids, such as release agents or wetting agents, may also be added to the reaction mixture.

The polymerization initiator is preferably included in the hydrogel or silicone-containing hydrogel monomer mixture. Such initiators may also be used in coating compositions, but are not preferred. The coating composition and the monomer mixture initiator may be the same or different. The polymerization initiator used may be visible light, heat, ultraviolet initiator, or the like or combinations thereof. These initiators are known in the art and are commercially available. The initiator can be used in an effective amount of a catalyst which is an amount sufficient to initiate the desired polymerization reaction. Generally, from about 0.1 to about 2 parts by weight per 100 parts of hydrogel or silicone hydrogel will be used.

The monomer mixture is dispersed in the coated mold. The hydrogel or silicone-containing hydrogel monomer mixture may be dispersed in a mold or semi-mould in a convenient manner including, but not limited to, pipetting, dispersion through syringes, pumping through automated or manual pumps, and the like, and combinations thereof. Can be. In the next step of the invention, the hydrogel or silicone-containing hydrogel monomer mixture is cured or polymerized to form a coated article. The residence time or the elapsed time during which the monomer mixture is dispersed in the mold until the start of curing is important because the coating composition is soluble in the hydrogel and silicone-containing hydrogel monomer mixture. The residence time should be less than about 5 minutes, preferably less than about 45 seconds.

Curing is further carried out under conditions suitable for curing of the coated article to be formed. Suitable conditions will vary, but are not limited to, depending on a number of factors including the amount and type of coating composition and monomers used, the product formed and the curing properties used, ie visible light or heat. Determination of the exact conditions required is at the discretion of those of ordinary skill in the art.

Curing of the monomer mixture can be initiated by appropriate selection of heat, visible or ultraviolet light or other means, preferably carried out in the presence of a polymerization initiator. When producing contact lenses, the preferred initiator is a 1: 1 blend of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, with preferred polymerization The starting method is visible light. In the case of some monomer reaction mixtures, it is preferred to cure the reaction mixture at a temperature slightly above room temperature, for example 25 to 90 ° C., in order to prevent phase separation of the components. In a particularly preferred embodiment for making contact lenses, the reaction mixture is precured at about 45 ° C. and then fully cured at about 70 ° C.

The resulting product may be coated with a coating composition coated on the mold surface of the mold. After curing the monomer mixture and coating composition, the resulting product is treated with a solvent to remove all diluents or traces of unreacted components used and the polymer is hydrated to form a hydrogel. In the case of contact lenses, the solvent used may be an aqueous solution such as water or physiological saline.

Or, depending on the solubility characteristics of the diluent used in the manufacture of the lens and the solubility characteristics of the residual unpolymerized monomer, the solvent used initially may be an organic liquid such as ethanol, methanol, isopropanol, mixtures thereof, or the like. It may be a mixture of one or more such organic liquids with water, and then extracted with pure water (or physiological saline) to make a hydrogel or silicone hydrogel lens swollen with water.

In a preferred embodiment, the silicone-containing hydrogel lens is prepared by dispersing in a mold or semi-mould, and then curing the macromer with a reaction mixture comprising the silicone-containing monomer and the hydrophilic monomer. This technique allows for a high degree of control of the final product structure.

The macromers can be prepared by combining (meth) acrylate and silicone, preferably in the presence of a group transfer polymerization ("GTP") catalyst. These macromers usually comprise a copolymer of various monomers. They can be formed in such a way that the monomers are present together in unique blocks or generally in a random distribution. These macromers may further be linear, branched or star shaped. The side chain structure is formed when a crosslinkable monomer such as polymethacrylate or 3- (trimethylsiloxy) propyl methacrylate is included in the macromer. Initiators, reaction conditions, monomers and catalysts that can be used in the preparation of GTP polymers are described, for example, in "Group-Transfer Polymerization" by O.W. Webster, in Encyclopedia of Polymer Sciences and Engineering Ed. (John Wiley & Sons) p. 580, 1987 is known. This polymerization is carried out under anhydrous conditions. Hydroxyl functional monomers such as HEMA can be introduced into the hydrolysis as their trimethylsiloxy esters to form free hydroxyl groups after polymerization. GTP provides the ability to assemble macromers with control of molecular weight distribution and monomer distribution over the chain. This macromer is then reacted with a reaction mixture mainly comprising polydimethylsiloxane (preferably mPDMS) and hydrophilic monomers.

Preferred macromer components include mPDMS, 3-methacryloxypropyltris (trimethylsiloxy) silane ("TRIS"), methyl methacrylate, HEMA, DMA, methacrylonitrile, ethyl methacrylate, butyl methacrylate, 2-hydroxypropyl-1-methacrylate, 2-hydroxyethyl methacrylamide and methacrylic acid. Macromers are more preferably made of a mixture comprising HEMA, methyl methacrylate, TRIS and mPDMS. The macromers comprise about 19.1 mol of trimethylsilyl ester of HEMA, about 2.8 mol of methyl methacrylate, about 7.9 mol of TRIS and about 3.3 mol of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane, or in fact It is most preferred to be made of these or a reaction mixture consisting of these, and using the dibutyltin dilaurate as catalyst, the above-mentioned material is converted to 3-isopropenyl-ω, ω-dimethylbenzyl isocyanate about 2.0 mol / React with mol to complete.

Silicone-containing hydrogels can be prepared by reacting a blend of macromers, monomers and other additives such as UV blockers, colorants, internal wetting agents and polymerization initiators. The reaction components of these blends usually include blends of hydrophobic silicones and hydrophilic components. Because these components are often immiscible due to their polarity differences, it is particularly advantageous to introduce hydrophobic silicone monomers into the macromers in combination with hydrophilic monomers (particularly monomers having hydroxyl groups). The macromer can then be used to mix additional silicone and hydrophilic monomers introduced into the final reaction mixture. These blends usually further contain a diluent for further mixing and dissolving all components. Preferably, the silicone based hydrogel is prepared by reacting the following monomer mixture: macromers, Si _8-10 monomethacryloxy terminated polydimethyl siloxane and hydrophilic monomers with trace amounts of additives and photoinitiators. Hydrogels are more preferably prepared by reacting macromers, Si _8-10 monomethacryloxy terminated polydimethyl siloxane, TRIS, DMA, HEMA and tetraethyleneglycol dimethacrylate (“TEGDMA”). Hydrogels (all amounts are calculated as weight percent based on the total weight of the formulation) macromers (about 18%), Si _8-10 monomethacryloxy terminated polydimethyl siloxanes (about 28%), TRIS (about 14%), DMA (about 26%), HEMA (about 5%), TEGDMA (about 1%), and polyvinylpyrrolidone ("PVP") (about 5%) with 20 weights of dimethyl-3-octanol diluent Prepared by reaction with trace additives and photoinitiators in the presence of%.

If present, the preferred range of the blended silicone-containing monomer of formula I and the additional silicone-containing monomer in the reaction mixture is from about 5 to about 100% by weight, more preferably based on the weight of the reactive component in the reaction mixture. About 10 to about 90 weight percent, most preferably about 15 to about 80 weight percent. When present, the preferred range of any hydrophilic monomer in the present invention is from about 5 to about 80 weight percent, more preferably from about 10 to about 60 weight percent, most preferred based on the weight of the reactive components in the reaction mixture. Preferably from about 20 to about 50% by weight. The preferred range of diluent is from about 0 to about 70 weight percent, more preferably from about 0 to about 50 weight percent, most preferably from about 0 to about 20 weight percent, based on the weight of the total reaction mixture. The amount of diluent required depends on the nature and relative amounts of the reactive components.

In a preferred combination of the reactive component, about 10 to about 60 weight percent, more preferably about 15 to about 50 weight percent, based on the weight of the reactive component is a silicone containing monomer, and based on the weight of the reactive component 20 to about 50 weight percent is a silicone containing monomer of formula (I), and about 10 to about 50 weight percent is hydrophilic monomer, more preferably DMA, based on the weight of the reactive component, and about 0.1 to about 1.0% by weight is UV or preferably visible light active photoinitiator, and from about 0 to about 20% by weight based on the weight of the total reaction mixture is a secondary or tertiary alcohol diluent, more preferably tertiary alcohol. to be.

Mold materials useful in the present invention are those that are unreactive with the coating composition and monomer mixture used. Preferably, the mold materials are polyolefins (such as polypropylene), and cyclic polyolefins (such as those sold under the trademark TOPAS ^R ).

The invention will be further elucidated with reference to the following non-limiting examples.

In the examples, the following abbreviations are used.

Bluewoo HEMA: Product wherein one chloride of the reactive bluewoo # 4 dye is base promoted substituted with hydroxyethyl methacrylate.

CGI 1850: 1: 1 (weight) blend of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylphenyl phosphine oxide

DMA: N, N-dimethylacrylamide

DOE-120: Polyethylene Glycol 120 Methyl Glucose Dioleate

EtOH: Ethanol

HEMA: 2-hydroxyethyl methacrylate

IPA: Isopropanol

mPDMS: monomethacryloxypropyl terminated polydimethylsiloxane

Norblock: 2- (2'-hydroxy-5-methacrylyloxyethylphenyl) -2H-benzotriazole

PVP: Poly (N-Vinyl Pyrrolidone)

TEGDMA: tetraethylene glycol dimethacrylate

TBACB: tetrabutyl ammonium-m-chlorobenzoate

THF: tetrahydrofuran

TMI: 3-isopropenyl-α, α-dimethylbenzyl isocyanate

TRIS: 3-methacryloxypropyltris (trimethylsiloxy) silane.

Example 1

A predominantly poly-DMA ("pDMA") subpolymer of DMA: HEMA (n = 70: n = 4) is prepared by group transfer polymerization and functionalized with TMI (n = 3) molar equivalents as follows. 40 g THF, tetrabutylammonium 3-chlorobenzoate (TBACB, 1M solution in THF, 0.31 ml, 0.00031 mol), 0.09 g bis (dimethylamino) -methylsilane, 0.7 g p-xylene and 2-trimethylsiloxyethyl meta 20.23 g (0.1 mol) of acrylate are charged to a dry three-necked flask under nitrogen. 4.36 g (0.025 mol) of methyltrimethylsilyl dimethylketone acetal is added to the mixture with stirring. The reaction is allowed to reach an exothermic peak and then cooled to 24 ° C. The solution is diluted with 82 g THF and 173.5 g (1.75 mol) of DMA are fed through a 100 ml syringe over 2 hours. The increase in exotherm is controlled below 55 ° C. by decreasing the feed rate of DMA and cooling the flask with ice. Additional TBACB (1M solution in THF, 0.94 ml, 0.00094 mol) diluted with 9 ml THF was slowly fed during the reaction. After the temperature was lowered back to 36 ° C., 160 g of dry THF was added to the solution. After a total reaction time of 4 hours 30 minutes, the reaction is quenched at 24 ° C. with a mixture of 3.6 g deionized water, 6.40 g methanol and 0.06 g dichloroacetic acid. The quenched solution is refluxed at 65 ° C. for 5 hours, and then the solvent is distilled off while toluene is added until the evaporation temperature reaches 110.3 ° C. To a toluene solution is added a mixture of 15.1 g (0.08 mol) of TMI and 0.98 g of dibutyl tin dilaurate, and the mixture is refluxed at 115 ° C. for 3 hours. The resulting solution is cooled, then filtered through a membrane and the solvent is evaporated under vacuum at 30-45 ° C.

Two coating formulations are prepared by dissolving the partial polymer in IPA at 25% by weight, based on the total weight of the solution, with 0.1% by weight of DOE-120 surfactant. Each coating is applied to the mold surface of the complementary half mold of the lens mold made of Topas ^R 5013. The coating is applied by compression molding about 3 μl of the coating solution onto the mold surface with a silicone pad. For the front curved mold surface, the pads are contacted with the coating, dropped on the mold surface, then compressed for about 0.5 seconds, held for 1 second, and released over about 2 seconds. For the back curved mold surface, the pad is dropped onto the mold surface, compressed and then released over about 0.5 seconds. The coating is dried at room temperature for 30 minutes. The average dry coating thickness differs from 1 to 2 μm based on thickness measurements on flat topas, as assessed using Atomic Force Microscopy (“AFM”).

The lens is cast by using a mold to disperse the silicone hydrogel lens material of the following formulation into the mold.                 

weight% Macromer 18.95 TRIS 14.74 DMA 27.37 MPDMS 29.47 NORBLOC 2.11 CGI 1850 1.05 TEGDMA 1.05 HEMA 5.26

100 parts of the aforementioned formulations are mixed with 20 parts of 3,7-dimethyl-3-octanol diluent.

Macromer Manufacturing

30.0 g (0.277 mol) of bis (dimethylamino) methylsilane, 1M solution of TBACB (TBACB 386.0 g in 1000 ml anhydrous THF) 13.75 ml, 61.39 g p-xylene (0.578 mol) in a dry container housed in an anhydrous box at ambient temperature under nitrogen ), Methyl methacrylate (1.4 equivalents to initiator) 154.28 g (1.541 mol), 2- (trimethylsiloxy) ethyl methacrylate (8.5 equivalents to initiator) 1892.13 g (9.352 mol) and THF 4399.78 g (61.01 mol) solution is added. Anhydrous three-neck round bottom flask equipped with thermocouple and condenser (both connected to nitrogen source) is charged with the above mixture prepared in anhydrous box.

The reaction mixture is cooled to 15 ° C. while stirring and purging with nitrogen. After the solution reaches 15 ° C., 191.75 g (1.100 mol) of 1-trimethylsiloxy-1-methoxy-2-methylpropene (1 equivalent) is injected into the reaction vessel. The reaction is exothermic to about 62 ° C., then 30 ml of a 0.40 M solution of 154.4 g of TBACB in 11 ml of dry THF are metered through the reaction residue. After the reaction temperature reached 30 ° C. and the metering was started, 467.56 g (2.311 mol) of 2- (trimethylsiloxy) ethyl methacrylate (2.1 equivalents to the initiator), n-butyl monomethacryloxypropyl- 3636.6 g (3.463 mol) of polydimethylsiloxane (3.2 equivalents to initiator), 3673.84 g (8.689 mol) of TRIS (7.9 equivalents to initiator) and 20.0 g of bis (dimethylamino) methylsilane are added.

The mixture is exothermic to about 38-42 ° C. and then cooled to 30 ° C. At this point, 10.0 g (0.076 mol) of bis (dimethylamino) methylsilane, 154.26 g (1.541 mol) of methyl methacrylate (1.4 equivalents to initiator) and 2-trimethylsiloxy) ethyl methacrylate (initiator) 8.5 equivalents) 1892.13 g (9.352 mol) of solution is added and the mixture is exothermic to about 40 ° C. The reaction temperature is lowered to about 30 ° C. and 2 gallons of THF are added to lower the viscosity. A solution of 439.69 g of water, 740.6 g of methanol and 8.8 g (0.068 mol) of dichloroacetic acid is added and the mixture is refluxed for 4.5 h to deblock the protecting group on HEMA. The volatiles are then removed and toluene is added to assist in the removal of water until the evaporation temperature reaches 110 ° C.

The reaction flask is maintained at about 110 ° C. and a solution of 443 g (2.201 mol) TMI and 5.7 g (0.010 mol) dibutyltin dilaurate is added. The mixture is allowed to react until the isocyanate peak disappears by IR. Toluene is evaporated under reduced pressure to yield an off-white anhydrous waxy reactive monomer. The macromer is placed in acetone (acetone vs. macromer 2: 1 by weight). After 24 hours, water is added to precipitate the macromer, the macromer is filtered and then dried at 45-60 ° C. for 20-30 hours using a vacuum oven.

The lens material is cured at 45 ° C. for about 30 minutes using visible light, then the lens is released, dissolved using 100% IPA and exchanged with fresh borate buffered saline solution. The time between when the lens material is dispersed in the mold and when the curing is started, or the residence time is less than 5 minutes in all cases.

The wettability of the lens is measured using a dynamic contact angle as follows. Five samples of each lens type are prepared by cutting the central strip about 5 mm wide and equilibrating the strip in a borate buffered saline solution for at least 30 minutes. The contact angle of the strip is measured using the Cahn DCA-315 microbalance. Each sample is cycled four times in borate buffered saline and the circulation is averaged to obtain the leading and return contact angles for each lens. The contact angles of the five lenses are then averaged to obtain an average contact angle for this set.

In the coated mold, the preceding contact angle of the lens is 65 ± 4 °. In the uncoated control mold, the leading contact angle is 99 ± 8 °. This demonstrates that the mold transfer coating significantly improved the wettability of the silicone hydrogel lens.

Examples 2-5

Free radical polymerization is used to prepare random copolymers of DMA and HEMA (n = 272 for DMA and n = 23 for HEMA) as follows. 100 mg of HEMA (300 mg, 2.31 mmol), DMA (29.7 g, 300 mmol) and CGI 1850 are dissolved in 120 ml of 3-methyl-3-pentanol. The mixture is evacuated for 10-15 minutes to completely degas the mixture and then purged with nitrogen. Exhaust / purging is repeated 3-4 times, then the mixture is placed under a nitrogen environment and transferred to a crystallization dish and covered with observation glass. The mixture is exposed to visible light, Phillips TL20 W / 03T bulbs over about 1 hour, then the system is exposed to oxygen to terminate the polymerization.

The mixture is diluted with hexanes to precipitate the resulting polymer. Further purification is carried out by dissolving the polymer in acetone and reprecipitating with hexane. The acetone / hexane sequence is repeated, the white polymer is washed thoroughly with hexane and then dried on a rotary evaporator and the product is cut into several small pieces before completion of drying. 27.0 g (90%) of a white foam like product are obtained.

A small amount of the above product is derivatized as its methacrylate using the following process. The 50 ml three-neck round bottom flask is heat dried in vacuo, placed under nitrogen, and then charged with 10 ml THF. Pyridine (5 ml) is added to the flask followed by 645 mg (7.5 mmol) of methacrylic acid. The system is cooled to below 5 ° C. and 1.026 g (9 mmol) of methanesulfonyl chloride is added dropwise to the solution over 5 to 10 minutes. The mixture is further stirred for 10 minutes while warming to room temperature.

A 250 ml three-necked flask is charged with 9 g of HEMA / DMA copolymer and 9 mg of phenothiazine. The system is purged with nitrogen and 50 ml of THF is added to dissolve the compound. The mixed anhydride solution is added to the flask via syringe and the reaction mixture is stirred overnight at ambient temperature.

The solution is filtered through a sintered glass furnace to 200 ml of stirred hexane. The solvent is decanted off and the product is purified by dissolving in isopropyl acetate and then hexane is added. The polymer is washed twice with 50 ml of hexane and dried on a rotary evaporator. The high methacrylic acid content requires further purification. The product is dissolved in acetone and then precipitated using hexanes.

A coating formulation of 20 wt% pDMA / HEMA and 0.1 wt% DOW-120 in IPA was applied to the topas 5013 mold as in Example 1. The dry coating thickness measured by AFM exceeds 1 μm. Both natural polymers and functionalized (with methacrylate) polymers are examined as coatings. The lens is prepared using the silicone hydrogel lens material of Example 1, except the residence time is as described in Table 2 below. In addition, Table 2 shows the wettability of the coatings.

Example Methacrylate cloth Residence time Leading contact angle (°) 2 Yes 15 minutes 87 3 Yes 2.5 minutes 58 4 Yes 45 sec 62 5 no 45 sec 82

The results demonstrate that a level of wetting of acceptance or a prior contact angle of less than 90 ° can be obtained with or without methacrylate groups. In addition, the results indicate that the contact angle depends on the residence time and the highest wettable lens is produced in less than 2.5 minutes.

Examples 6-9

Poly-HEMA coatings are evaluated for efficacy and wettability. The coating is prepared by exposing a solution of MEMA, Bluewoo HEMA and IRGACURE 1850 in ethylene glycol to low intensity visible light, ie Philips TL20 W / 03T bulb, using a curing time of 1-2 hours. The polymer is separated by aqueous work up followed by several aqueous washes to remove unreacted components. Polymer molecular weights of less than about 300 kD were found to be unsuitable for use as coating polymers in the lens material of Example 1. Poly-HEMA of 360 kD MW, available from Aldrich Chemical Company, has been successfully used as a coating. Coating formulations with different concentrations of poly-HEMA are prepared as follows.

Poly-HEMA: Water: Ethanol: DOE-120 = 10: 20: 70: 0.1 w / w

Poly-HEMA: water: ethanol: DOE-120 = 15: 20: 65: 0.1 w / w

Poly-HEMA: water: ethanol: DOE-120 = 20: 20: 60: 0.1 w / w

The coating is applied to the mold surface of the Topas 5013 mold according to the process of Example 1, except that the mold is treated with air plasma for less than 0.5 seconds prior to coating to improve diffusion of the coating solution into the mold. The lens is manufactured using the process of Example 1 and the silicone hydrogel lens material, except that the residence time is 45 seconds.

The coated lens obtained is tested for wettability using dynamic contact angle and for surface roughness using AFM. AFM images are obtained by contact mode AFM using 0.06N / m SiN ₄ cantilever imaging in borate buffered saline solution. Images are minimized prior to data acquisition, usually less than 10 nN. The image is produced 20 × 20 μm in the optical region and over the anterior surface of each lens. Two lenses are evaluated for a total of six images. Average peak-to-peak roughness values are calculated using 24 10 × 10 μm portions from these images. Peak to peak roughness is defined as the height difference between the lowest and highest points in the tested part. The results are shown in Table 3.

Example % Poly-HEMA in coating Leading contact angle (°) Average peak-to-peak roughness (nm) 6 0 107 <100 7 10 65 1425 8 15 46 3276 9 20 48 N / A

The results demonstrate that wettability improves with increasing concentration of poly-HEMA in the coating solution. In addition, the surface roughness increases with increasing poly-HEMA content, and the 20% by weight poly-HEMA lens was too high and could not be analyzed. 10 weight percent poly-HEMA produces a dry coating thickness of about 200 nm on the mold. The target peak-to-peak roughness for useful lenses is less than 500 nm, and therefore the dry coating thickness must be substantially less than 200 nm to achieve a pass level of surface roughness while maintaining the desired wettability.

Examples 10 to 13

The silicone hydrogel lens material of Example 1 produces a lens having a water content of about 31%. Another similar lens formulation with 39% water content is as follows.

weight% Macromer 18 TRIS 14 DMA 26 MPDMS 28 TEGDMA One HEMA 5 PVP 5 Norblock 2 CGI 1850 One

The rest of the formulation is an additive and diluent. The monomer to diluent ratio is 100: 20 and the diluent is 3,7-dimethyl-3-octanol. Lenses of this material were coated with a 300 kD poly-HEMA coating, but the wettability and surface roughness obtained were rejected.

High molecular weight poly-HEMA containing 1.6% by weight or more of Bluewoo HEMA is synthesized using visible light disclosed by CGI 1850, and the resulting polymer has a molecular weight greater than 1,000,000. A mixture of 900 mg blue cow HEMA, 44.1 g HEMA, 651 mg CGI 1850 and 150 ml ethylene glycol is stirred until homogeneous and the system is degassed as described in Examples 2-5. The mixture is transferred to a large crystallization dish and covered with observation glass. The polymerization of the olefinic residues is carried out under visible light for about 1 hour. Oxygen is used to quench the polymerization and the mixture is poured into 500 ml of borate buffered saline solution and stirred for several hours until the material is converted to a more rigid form. The liquid is decanted off and the product is further washed with 500 ml of borate buffered saline solution. The polymer is cut into several small pieces and stirred in 500 ml of deionized water for at least 1 hour until the product is gel-like and hardly soluble in the solvent. The mixture is then diluted with a small amount of borate buffered saline solution to better precipitate the polymer. The mixture is filtered and washed with deionized water until the material is no longer dissolved. The suspension is filtered, dried on a rotary evaporator, cut into smaller pieces and further dried until crystalline and anhydride appears. The dark blue polymer is then ground into fines and each wash is further washed with deionized water with stirring for 1-2 hours. The wash lasts until little or no blue is observed in the solution, the product is filtered off, dried under reduced pressure and polished with a blender. The Mw of this coating polymer measured using GPC is 1,200,000 g / mol and the 2% solution of the polymer in 1: 1 ethanol: ethyl lactate solvent has a viscosity of 17.7 cP at a shear rate of 40 / s at 25 ° C.

The coating is used to coat the topas 5013 mold by spin coating according to the following process. 0.5 to 2 weight percent polymer solution is dissolved in 0.5 weight percent steps in a mixed solvent system of 1 part ETOH and 1 part ethyl lactate. The coating is applied to the mold surface of the mold by dispersing the solution at the partial spinning center at about 6000 rpm and spinning the portion for 5 seconds before stopping. Lenses are made from these coated molds using the lens materials described above and a residence time of 30 seconds. Table 5 shows the wettability and surface roughness of the lenses obtained.

Example % Poly-HEMA in coating Leading contact angle (°) Dry film thickness (nm) ^* Average peak-to-peak roughness (nm) 10 0.5 100 21 113 11 1.0 81 67 401 12 1.5 72 78 790 13 2.0 78 125 1170

* Measured by AFM on topas plate.

The results show that a change in dry film thickness can achieve both wettability and surface roughness of the pass level.

Example 14

The formulations described in Table 6 form high molecular weight Bluewoo poly-HEMA coated silicone hydrogel lenses.

weight% Macromer 17.98 TRIS 14.00 DMA 26.00 MPDMS 28.00 TEGDMA 1.00 HEMA 5.00 PVP 5.00 Norblock 2.00 Bluewoo HEMA 0.02 CGI 1850 1.00

The rest of the formulation is an additive and diluent. The ratio of monomer to diluent is 100: 20 and the diluent is 3,7-dimethyl-3-octanol. Acetic acid (1% of the final mixture) is used to stabilize the monomers.

The front and rear curved molds of Topas 5013 were coated with a 1.25 wt% solution of Bluewoo Poly-HEMA and the lenses were prepared as described in Examples 10-13. Excess coating accumulated near the edge of the front surface mold is wiped with a cloth during the spinning process.

The lens is tested for wettability and surface roughness prior to clinical evaluation. The average peak to peak front surface roughness is 291 nm and the average preceding contact angle is 83 °. Five lenses with -0.50 diopters of optics are suitable for a 30-minute wear schedule whereas the parallel-parallel study. The lens surface is equivalent in ocular wetting or tearing time and deposition resistance to ACUVUE ^R Etafilcon A lenses, demonstrating that applying a coating to the lens yields a physiologically compatible lens.

Claims (51)

Coating the surface of the mold or mold half with 2-20 μl of high molecular weight coating composition (a), (B) dispersing a mixture comprising a hydrogel monomer, a silicone-containing hydrogel monomer or a combination thereof in a mold or semi-mould; and And (c) curing the monomer mixture and the coating composition using a residence time of less than 5 minutes under conditions suitable for forming the article coated with the coating composition. The method of claim 1 wherein the article is a contact lens. The method of claim 1 or 2, wherein the monomer mixture comprises a hydrogel. The method of claim 1 or 2, wherein the monomer mixture comprises silicone hydrogel monomers. The method of claim 1 wherein the molecular weight of the coating composition is greater than 300 kD. The method of claim 1 wherein the residence time is less than 45 seconds. The method of claim 5, wherein the residence time is less than 45 seconds. The method of claim 1 wherein the coating composition further comprises a low boiling point solvent and a high boiling point solvent. The method of claim 8, wherein the coating of the mold surface is performed by spin coating. delete 10. The method of claim 9, further comprising applying a pressurized air jet to the edge of the mold following the spin coating step. 10. An article made by the method according to any one of claims 1, 6, 7, and 9. A contact lens made by the method according to claim 2. Coating the surface of the mold or half mold with 2-20 μl of high molecular weight hydrophilic coating composition (a), (B) dispersing a mixture comprising a hydrogel monomer, a silicone-containing hydrogel monomer or a combination thereof in a mold or semi-mould; and And (c) curing the monomer mixture and the coating composition using a residence time of less than 5 minutes under conditions suitable for forming the article coated with the coating composition. The method of claim 14 wherein the article is a contact lens. The method of claim 15, wherein the monomer mixture comprises a hydrogel monomer. The method of claim 15, wherein the monomer mixture comprises a silicone hydrogel monomer. The method of claim 14, wherein the residence time is less than 45 seconds. 18. The method of claim 17, including the silicone hydrogel monomer mixture, Si _8-10 mono methacryloxypropyl-terminated polydimethylsiloxane, Si _8-10 mono methacryloxypropyl-terminated polydimethyl siloxane and polydimethyl siloxane other than the hydrophilic monomer And a reaction product of the polymerizable mixture with a silicone-based macro group transfer polymerisation product. The method of claim 19, wherein the silicone hydrogel monomer mixture is 15 to 25% by weight of macromer, 20 to 30% by weight of Si _8-10 monomethacryloxy terminated polydimethyl siloxane, methacryloxypropyl tris (trimethyl siloxy) silane 15 to 25% by weight, 20 to 30% by weight of N, N-dimethyl acrylamide, 2 to 7% by weight of 2-hydroxyethyl methacrylate, 0 to 5% by weight of tetraethylene glycol dimethacrylate and poly (N- Vinyl pyrrolidinone) from 0 to 5% by weight. 21. The coating composition of claim 14, wherein the coating composition is poly (vinyl alcohol), polyethylene oxide, poly (2-hydroxyethyl methacrylate), poly (acrylic acid), poly (methacrylic acid), Poly (maleic acid), poly (itaconic acid), poly (acrylamide), poly (dimethylacrylamide), carboxymethylated polymers, polystyrene sulfonic acids, polysulfonate polymers, polysaccharides, glucose amino glycans, blocks thereof Or random copolymers, or mixtures thereof. The method of claim 21, wherein the coating composition comprises poly (2-hydroxyethyl methacrylate). The method of claim 15, wherein the coating composition further comprises a low boiling point solvent and a high boiling point solvent. The method of claim 23, wherein the coating of the mold surface is performed by spin coating. delete 25. The method of claim 24, further comprising applying a pressurized air jet to the edge of the mold following the spin coating step. An article made by the method according to claim 14. A contact lens made by the method according to any one of claims 15, 18, 19 and 20. A contact lens made by the method according to claim 21. A contact lens made by the method according to claim 22. Coating the surface of the mold or half mold with 2-20 μl of a hydrophilic coating composition having a molecular weight greater than 300 kD (a), (B) dispersing a mixture comprising a hydrogel monomer, a silicone-containing hydrogel monomer or a combination thereof in a mold or semi-mould; and (C) curing the monomer mixture and coating composition using a residence time of less than 45 seconds under conditions suitable for forming a contact lens coated with the coating composition. The method of claim 31, wherein the monomer mixture comprises a hydrogel monomer. 32. The method of claim 31, wherein the monomer mixture comprises silicone hydrogel monomers. 35. The method of claim 33, including the silicone hydrogel monomer mixture, Si _8-10 mono methacryloxypropyl-terminated polydimethylsiloxane, Si _8-10 mono methacryloxypropyl-terminated polydimethyl siloxane and polydimethyl siloxane other than the hydrophilic monomer Reacting the polymerizable mixture with a silicone-based macromer group transfer polymerization product. 35. The silicone hydrogel monomer mixture according to claim 34, wherein the silicone hydrogel monomer mixture is 15-25 wt% of macromer, 20-30 wt% of Si _8-10 monomethacryloxy terminated polydimethyl siloxane, methacryloxypropyl tris (trimethyl siloxy) silane 15 to 25% by weight, 20 to 30% by weight of N, N-dimethyl acrylamide, 2 to 7% by weight of 2-hydroxyethyl methacrylate, 0 to 5% by weight of tetraethylene glycol dimethacrylate and poly (N- Vinyl pyrrolidinone) from 0 to 5% by weight. 36. The coating composition of any one of claims 31 to 35 wherein the coating composition is selected from the group consisting of poly (vinyl alcohol), polyethylene oxide, poly (2-hydroxyethyl methacrylate), poly (acrylic acid), poly (methacrylic acid), Poly (maleic acid), poly (itaconic acid), poly (acrylamide), poly (dimethylacrylamide), carboxymethylated polymers, polystyrene sulfonic acids, polysulfonate polymers, polysaccharides, glucose amino glycans, blocks thereof Or random copolymers, or mixtures thereof. 37. The method of claim 36, wherein the coating composition comprises poly (2-hydroxyethyl methacrylate). 37. The method of claim 36, wherein the coating composition further comprises a low boiling point solvent and a high boiling point solvent. The method of claim 38, wherein the coating of the mold surface is performed by spin coating. delete 40. The method of claim 39, further comprising applying a pressurized air jet to the edge of the mold following the spin coating step. A contact lens made by the method according to any one of claims 31 to 35. A contact lens made by the method of claim 36. A contact lens made by the method of claim 37. A contact lens made by the method according to claim 38. A contact lens made by the method of claim 39. 43. The contact lens of claim 42, wherein the coating composition comprises a coating having a dry film thickness of 5 to 70 nm. 44. The contact lens of claim 43, wherein the coating composition comprises a coating having a dry film thickness of 5 to 70 nm. 45. The contact lens of claim 44, wherein the coating composition comprises a coating having a dry film thickness of 5 to 70 nm. 46. The contact lens of claim 45, wherein the coating composition comprises a coating having a dry film thickness of 5 to 70 nm. 47. The contact lens of claim 46, wherein the coating composition comprises a coating having a dry film thickness of 5 to 70 nm.